The world’s growing population results in increased energy needs that cannot yet be fully supported by the renewable sources of energy. These modern conditions and restraints have created the need to further research methods to enhance the recovery of resources previously unavailable due to technical and/or economic reasons and to reduce the environmental impacts of using fossil fuels. In this dissertation, applications of electrokinetic phenomena for the improvement of subsurface energy resource extraction are investigated using experimental and numerical tools. Electrodialysis is proposed as a method of pre-treatment of the flow-back water produced during fracturing stage of shale gas extraction. The method targets the reduction of Total Dissolved Solids levels in the flow-back water so that it can either be treated further or be reused directly. The treatment and reuse of the flow-back water can potentially improve the sustainability of the shale gas extraction, controlling the amounts of water used and the general environmental footprint of the process. In addition, the electrically assisted oil recovery is investigated as a potential technique for the enhancement of oil extraction, especially for the case of heavy crude oil. The high viscosity and low mobility of heavy crude oil render it almost impossible or not economical to extract. The method uses the application of low electrical field (direct current) to the oil reservoir to facilitate and increase the oil recovery by taking advantage of the mechanisms involved in electrokinetic phenomena.

This master´s thesis deals with trade with crude oil and its impact on the world economy. Everyone, who wants to start to trade with crude oil, should find out basic terminology and information about crude oil that is characterized in the first chapter. The hunt for oil started many years ago, therefore the history is also mentioned in this master´s thesis. The second chapter focuses on the world trade with crude oil. Territorial structure and trade flows are described in this part of the master´s thesis. Nevertheless, the crude oil also has an impact on the world economy and economies of single states. The third chapter analyses states, where the inhabitants live beyond means of people from other countries but these states are so depended on crude oil that if this trade stopped, these countries would go bankrupt. However, there are also exceptions. Even though, there are states that have huge sources of crude oil, they still have to deal with financial problems. The forth chapter characterizes the trade with crude oil of the Czech Republic because it is a net importer of crude oil and the last chapter focuses on new trends in crude oil such as shale oil and trading at a crude oil market.

Orientador: Maria Regina Wolf Maciel / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-24T13:22:45Z (GMT). No. of bitstreams: 1 Borges_FabioLuiz_M.pdf: 1928972 bytes, checksum: 8ee551cc8034ad570e84bd024b3702ca (MD5) Previous issue date: 2014 / Resumo: Essa dissertação tem como objetivo avaliar a utilização de curvas de destilação simulada de petróleo analisadas por dois métodos cromatográficos (ASTM D7169 e DHA Front End) combinados em um modelo de predição de rendimentos de derivados de uma unidade de destilação atmosférica e a vácuo. Os métodos utilizados são de execução mais ágil e de custo bastante reduzido em relação aos métodos de obtenção de curvas de Ponto de Ebulição Verdadeiro (PEV), sendo viável obter curvas de destilação de tanques de petróleo em laboratórios de refinarias. A utilização dessas análises possibilita a obtenção de curvas das cargas a serem processadas mais representativas do que as curvas obtidas utilizando as curvas PEV disponíveis no BDAP (Banco de Dados de Avaliação de Petróleos da Petrobras) em conjunto com a proporção de petróleos informada pelo BDEMQ (Banco de Dados de Estoque, Movimentação e Qualidade da Petrobras) em cada tanque. Para realizar essa avaliação, foi elaborada, no software PETROSIM®, uma simulação do tipo Distop, a qual foi calibrada utilizando-se as vazões e as curvas de destilação dos derivados amostrados em uma das plantas de destilação da Refinaria de Paulínia. Em seguida, foram coletadas amostras de tanques de petróleo, as quais foram analisadas pelos dois métodos combinados para obter as curvas de destilação, que foram utilizadas como dados de entrada da simulação calibrada, obtendo os rendimentos dos derivados. Foram também obtidos os rendimentos da mesma simulação calibrada utilizando como dados de entrada os dados de curvas PEV disponíveis no BDAP e também pelo método de predição baseado em rendimentos fixos de petróleos, que são gerados pelo software Blend-BR®, de propriedade da Petrobras, cujos dados de entrada também são as curvas PEV do BDAP. Os rendimentos obtidos por esses três métodos foram comparados com os rendimentos obtidos na unidade quando os tanques de petróleo amostrados foram processados. Os resultados obtidos indicaram que a simulação calibrada utilizando os dados analisados pelos métodos cromatográficos forneceu rendimentos mais aderentes aos realizados do que os outros métodos, principalmente na predição de rendimentos de nafta / Abstract: This thesis aims to evaluate the use of crude distillation curves analyzed by two combined chromatographic methods (ASTM D7169 and DHA Front End) combined into an atmospheric and vacuum crude distillation unit yields prediction model. These methods are faster to be executed and have the costs pretty lower compared to the methods used to obtain the True Boiling Point (TBP) curves, enabling to obtain distillation curves of crude tanks in refinery laboratories. These analyzes enable obtaining curves of the loads to be processed more representative than the curves obtained using the TBP curves available in BDAP (the Petrobras petroleum Database) and the proportion of oils informed by BDEMQ (the Petrobras feedstocks and quality Database) for each tank. To perform this evaluation, it was built in PETROSIM® software a Distop simulation, which was calibrated using flow rates and crude cuts distillation curves from the samples collected at on of the crude distillation units of Paulínia Refinery. Samples of oil tanks, which were analyzed by the two combined methods to obtain the distillation curves, were then used as input data the calibrated simulation, obtaining the crude cuts yields. The cuts yields were also obtained by the same calibrated simulation using as input data TBP curves available at BDAP and also by a model based on fixed crude cuts yields, which are performed by the software Blend-BR®, property of Petrobras, whose data input are also the TBP curves available at BDAP. The yields obtained by these three methods were compared with the yields obtained in the industrial unit when the sampled oil tanks were processed. The results indicated that the calibrated simulation using data analyzed by the chromatographic methods provided yields that are closer to actual ones than other methods, especially for the naphtha yields / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Orientador: Marcos Nogueira Eberlin / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T06:50:00Z (GMT). No. of bitstreams: 1 Pudenzi_MarcosAlbieri_M.pdf: 6732140 bytes, checksum: 0b8176e8c477d9dca874d72376dfcae5 (MD5) Previous issue date: 2015 / Resumo: Esse trabalho tem como objetivo conhecer e avaliar a ionização dos compostos polares no petróleo for Espectrometria de Massas por Ressonância Ciclotrônica de Íons com Transformada de Fourier (FTICR MS do inglês Fourier Transform Ion Cyclotron Resonance Mass Spectrometry), relacionando essa ionização com parâmetros experimentais e características intrínsecas das moléculas. No Capítulo 1 o tipo de amostra de interesse (petróleo) é abordado, tanto em suas características quanto em sua análise, definindo petroleômica e sua função. A espectrometria de massas é apresentada, então, como ferramenta de grande utilidade nos estudos petroleômicos, em especial aquela de ultra alta resolução como FTICR MS (Fourier Transform Ion Cyclotron Resonance Mass Spectrometry) acoplada a fonte de ionização eletrospray (ESI). No Capítulo 2 a ferramenta estatística do planejamento de experimentos é apresentada e, então, utilizada em uma amostra real de petróleo de forma a relacionar os parâmetros operacionais da fonte de ESI com respostas avaliadas comumente em petroleômica. Aspectos interessantes das relações parâmetro-resposta surgem durante o estudo, mostrando que a análise de petróleo por ESI-FTICR MS, apesar de largamente utilizada na literatura, não é trivial e precauções devem ser tomadas durante a otimização dos parâmetros experimentais. No Capítulo 3 as técnicas de APCI (Atmospheric Pressure Chemical Ionization) e APPI (Atmospheric Pressure PhotoIonization) são abordadas e utilizadas, juntamente com ESI, para avaliar a ionização de padrões de compostos similares àqueles encontrados nas principais classes de compostos polares do petróleo. A análise pelas técnicas que ionizam de forma mais abrangente os compostos apresentaram comportamentos que tornam tais análises inviáveis. Uma reação de metilação que melhora a ionização de compostos sulfurados também é realizada em duas condições, comparando-se tais condições a partir dos espectros obtidos após suas análises. Conhecendo a ionização desses compostos padrões, é possível entender a petroleômica de forma mais ampla dando maior confiabilidade para estabelecer as relações composição-comportamento do petróleo / Abstract: The aim of this work is to know and evaluate the crude oil polar compounds ionization through Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, relating this ionization with experimental parameters and intrinsic characteristics of molecules. On Chapter 1 the sample of interest (crude oil) is addressed, both in its characteristics and its analysis, defining petroleomics and its function. Mass spectrometry is then presented as a tool of great utility in petroleomic studies, in special the ultra high resolution one as FTICR MS coupled to eletrospray Ionization (ESI). On Chapter 2 the design of experiment statistic tool is presented and used in a real crude oil sample in order to relate operational parameters of ESI source to commonly evaluated responses in petroleomics. Interesting aspects regarding parameter-response relationships arises during the study, showing that the crude oil analysis using ESI-FTICR MS, while it is largely used in literature, it is not trivial and precautions have to be taken during the optimization of experimental parameters. On Chapter 3 APCI (Atmospheric Pressure Chemical Ionization) and APPI (Atmospheric Pressure PhotoIonization) technics are addressed and used, along with ESI, to evaluate the ionization of standard compounds similar to those polar compounds found in crude oil. Analysis using sources that ionizes in the most comprehensive way has shown such behavior that makes the analysis unviable. A methylation reaction that improves the ionization of sulfur compounds is also made on two conditions, comparing these conditions through the obtained spectra after their analysis. By knowing the ionization of these standard compounds it is possible to understand the petroleomics in a much comprehensive way, providing reliability to stablish composition-behavior relations of crude oil / Mestrado / Quimica Organica / Mestre em Química

>Magister Scientiae - MSc / The global dependence on non-renewable fossil fuels to meet energy needs cannot be sustained for a long time and it is already evident in the escalation of fuel prices over the past decade. This research was performed towards renewable energy production from agricultural and food waste. The use of agricultural and food waste has benefits such as being grown in a land that is not in competition with food crops protein, all year round availability, and having high lipid content. The produced bio-crude oil can be upgraded to remove moisture and acidity level, and can be used as a substitute for heavy oils such as diesel to power static appliances or can be used as petrol distillate fuel alternative. Hydrothermal liquefaction (HTL) process is one of the commonly used technologies for converting agricultural and food waste into liquid biofuels.

This study attempted to determine hydrocarbons in the crude oil by comparing the results obtained using the two methods of analysis: chemical analysis and Kurtz-Headington analysis. The Kurtz-Headington analysis was found to be adequate to determine hydrocarbons in the crude oil.

Crude glycerol is the major byproduct of the biodiesel industry. There is an abundance of this byproduct and purifying it for use in industries such as food, pharmaceutical, or cosmetic is prohibitively expensive. Developing an alternative use for crude glycerol is needed. Utilizing it as a carbon source in the fermentation of algae is one potential method for using this under-utilized byproduct. In this research, crude glycerol is used in the mixotrophic production of the alga, Phaeodactylum tricornutum, which is an eicosapentaenoic acid (EPA) producing diatom. Mixotrophic growth is when cells perform autotrophic and heterotrophic modes of growth concurrently. EPA is an omega-3 polyunsaturated fatty acid that has been demonstrated to have a multitude of beneficial health effects, including maintaining human cardiovascular health, treating cancer and human depression diseases, and an anti-obesity effect. In this study, the potential of using crude glycerol in batch mode mixotrophic culture of P. tricornutum was investigated. Once the mixotrophic culture was established, parameters involved in increasing the biomass and EPA production were optimized. These included nitrogen source, level of supplemental carbon dioxide, and concentration of crude glycerol. Using nitrate, 0.08 M crude glycerol, and 3% (vol/vol) carbon dioxide led to the highest biomass productivity of 0.446 g L?? day?? and the highest EPA productivity of 16.9 mg L?? day?? in batch mode culture. The continuous culture of the mixotrophic culture was then performed following the batch culture optimization. The effects of dilution rate were observed in continuous culture with the parameters of nitrate as the nitrogen source, 0.08 M crude glycerol, and 3% (vol/vol) carbon dioxide held constant. The highest biomass productivity of 0.612 g L?? day?? was obtained at D = 0.24 day??. The highest EPA productivity of 16.5 mg L?? day?? was achieved at both D = 0.15 day?? and D = 0.24 day??. The maximum specific growth rate was estimated from the washing out dilution rate and was determined to be around 0.677 day??. Overall, it was found that crude glycerol increases the biomass and EPA productivity of Phaeodactylum tricornutum. Continuous culture with the use of crude glycerol can further increase these measurements. The potential for scaling up studies is demonstrated by these results and can help lead to a market for this abundant, little-used byproduct of the biodiesel industry. / Master of Science

Crude glycerol is a major byproduct if the biodiesel industry. Biodiesel manufacturers are currently facing the challenges of appropriate disposal of this waste material. Crude glycerol is expensive to purify for use in food, cosmetic, and pharmaceutical industries and therefore, alternative methods for use of this crude glycerol are needed. A promising alternative is to use this crude glycerol as a carbon source for microalgae fermentation. In this project, we investigated the use of crude glycerol as a less expensive substrate for the fermentation of the microalgae <i>Schizochytrium limacinum</i> and <i>Pythium irregulare</i> which are prolific producers of omega-3 polyunsaturated fatty acids. Omega-3 fatty acids have many beneficially effects on treating human diseases such as cardiovascular diseases, cancers, and neurological disorders. In addition, the omega-3 fatty acids docosahexaenoic acid (DHA) has been shown to be an important factor in infant brain and eye development. The first part of this study focused on the continuous fermentation of <i>S. limacinum</i>, a prolific producer of DHA. The objective of this study was to examine the algal cellular physiology and maximize its DHA productivity. Two important parameters used in continuous fermentation were studied: dilution rate (D) and feed glycerol concentration (S₀). The highest biomass productivity of 3.88 g/L-day was obtained at D = 0.3 day⁻¹ and S₀ = 60 g/L, while the highest DHA productivity (0.52 g/L-day) was obtained at D = 0.3 day⁻¹ and S₀ = 90 g/L. The cells had a true growth yield of 0.283 g/g, a maximum specific growth rate of 0.692 day⁻¹, and a maintenance coefficient of 0.2216 day⁻¹. The second part of this study focused on morphology issues with <i>P. irregulare</i>, a prolific producer of eicosapentaenoic acid (EPA). <i>P. irregulare</i> has a filamentous morphology, which can make fermentation difficult. The mycelium can stick to the agitation blades resulting in mechanical problems. In addition, this filamentous morphology prevents adequate amounts of oxygen from reaching some cells resulting in decreased productivities. The focus of this research was to control the fermentation conditions to make the algae grow in small pellets, a morphology more suitable for fermentation. In flask culture studies, pellets were formed at an agitation speed of 110 rpm in both regular and baffled flasks. Baffled flasks resulted in pellet formation at 90 and 130 rpm as well. Fermentation studies resulted in pellet formation at agitation speeds of 150 and 300 rpm. Pellets were better able to form when a baffle was not in place. In addition, agitation speed influenced pellet size, with smaller pellets forming at the higher agitation speed. Overall, this study showed that crude glycerol can be used as a carbon source for the continuous fermentation of <i>S. limacinum</i> with high DHA productivity and the morphology of <i>P. irregulare</i> could be controlled by manipulating culture conditions, mainly agitation speed. These results show the potential for scale-up studies for both algal species. / Master of Science

No / Petroleum contributes significantly to our lives and will continue do so for many years to come. Petroleum derivatives supply more than 50% of the world's total supply of energy (Jarullah, 2011). Traditionally crude oil goes though fractional distillation to produce different grades of fuel such as gasoline, kerosene, diesel oil, etc. providing fuel for automobiles, tractors, trucks, aircraft, and ships. Catalytic hydrotreating (HDT) is used to detoxify the oil fractions produced by fractional distillation in the petroleum refining industries which involve removal of pollutants such as sulfur, nitrogen, metals, and asphaltene in trickle bed reactors. Recently Jarullah and co-workers proposed detoxification of whole crude oil a priori before the crude oil enters further processing in a fractionating column. This chapter highlights this new technology.

The growing demand for high-quality middle distillates is increasing worldwide, whereas the demand for low-value oil products, such as heavy oils and residues, is decreasing. Thus, maximizing the production of more liquid distillates of very high quality is of immediate interest to refiners. At the same time, environmental legislation has led to more strict specifications of petroleum derivatives. Hydrotreatment (HDT) of crude oil is one of the most challenging tasks in the petroleum refining industry, which has not been reported widely in the literature. In this work, crude oil was hydrotreated upon a commercial cobalt¿molybdenum on alumina (Co¿Mo/¿-Al2O3) catalyst presulfided at specified conditions. Detailed pilot-plant experiments were conducted in a continuous-flow isothermal trickle-bed reactor (TBR), and the main hydrotreating reactions were hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeasphaltenization (HDAs), and hydrodemetallization (HDM), which includes hydrodevanadization (HDV) and hydrodenickelation (HDNi). The reaction temperature (T), the hydrogen pressure (P), and the liquid hourly space velocity (LHSV) were varied with certain ranges, with constant hydrogen to oil (H2/Oil) ratio. The effects of T, P, and LHSV on the conversion of sulfur, nitrogen, vanadium, nickel, and asphaltene were studied. The results showed that high T and P and low LHSV in HDS, HDN, HDV, HDNi, and HDAs of crude oil improve the sulfur (S), nitrogen (N), metals [vanadium (V) and nickel (Ni)], and asphaltene (Asph) conversion. The hydrotreated crude oil has been distilled into the following fractions: light naphtha (LN), heavy naphtha (HN), heavy kerosene (HK), light gas oil (LGO), and reduced crude residue (RCR), to compare the yield of these fractions produced by distillation after the HDT process to those produced by conventional methods (i.e., HDT of each fraction separately after the distillation). The yield of the middle distillate showed greater yield compared to the middle distillate produced by conventional methods. The properties of RCR produced using both methods are also discussed.